Lubricating composition



Patented Sept. 28, 1943 3 UNITED: STATES PATENT OFFICE LUBRICATING comrosrrron Carl F. Prutton, East Cleveland, Ohio, a'ssignor,

by inesne assignments. to The Lubri-Zol Development Corporation, Cleveland, Ohio, a comaration of Delaware No Drawing. Original application March 1, 1939,

Divided and this application January 8, 1940, Serial No. 312,859

' as Claims. (01. 252-54) Serial No. 259,230.

This application is a continuation in part of my copending applications Serial Nos. 737,070, filed July 26, 1934; 755,987, filed December 4, 1934; 96,537, filed August 17, 1936,- now Patent No. 2,150,079, and a division of 259,230, filed March 1, 1939, now Patent No. 2,282,343.

This invention relates, as indicated, to lubri cating compositions, and more particularly to when the lubricant is exposed to elevated temperatures, there is a tendency to form similar deposits. Such deposits cause similar dlmculties,

.and particularly in the case of heavily loaded compositions for use in connection with the luterials may deposit on the metal parts with which the lubricant comes in contact in the form of gummy, resinous, or varnish-like deposits, or they may remain, to some extent, suspended in the body of the lubricant and act as the basis for the accumulation of dirt, metallic particles, and other foreign matter to form sludge.

These deposits thicken the oil, increase friction, lower the general efliciency of the engine, and make necessary more frequent drainage and replacement of the lubricant. In aggravated form, they may even cause failure of an engine due to sticking of the pistons in the cylinders, or bearing failures resulting from plugged oil passages and the like.

In winter, the passage of small amounts of gasoline into the crankcase of an engine often results in the precipitation of "sludge materials which are particularly. objectionable since they hinder lubrication of the engine on starting, causingundue wear and starting trouble. Obviously,

' an'oil which does not sludge, under such conditions, would be especially desirable for. winter use. The frequent oilchanges necessary at all times of the year in order to keep an engine operating efficiently and without danger of injury are a major source of expense and annoyance. In the case of gear lubrication, particularly gears, cause damage to the gear teeth surfaces 'since the deposit is likely to cause mis-alignment when precipitated on the gear surfaces, or bearing failures when precipitated in the oil passages.

It has been discovered that the sludge? and other deposits which form in the lubricating oil on use contain two predominant components comprising (1) polymerized hydrocarbons and (2) more or less oxidized polymerized hydrocarbons. These components act as cementing agents for small particles of inorganic and insoluble materials, greatly impairing the lubricating effect of the 'oil. I have found that the best solvents for one component of these deposits are not the best for the other. For addition to a lubricating oil it is obvious that solvents must be found which are mutually compatible, soluble or miscible in the oil, and which will dissolve the two com-. ponents of the deposits previously referred to. By lubricating oils are meant mineral oils or their synthetic equivalents.

It is,-therefore, among the objects of this invention to provide a lubricant which will not readily lose its lubricating qualities and sufler other deterioration due to s1udge" formation.

Anoth'erobject of this invention is to provide a lubricating composition which will not readily lose its lubricating qualities due to sludge formatipn and will also have extreme pressure characterlstlcs.

It is also among the objects of'this invention to provide a lubricating mineral oil which will resist deteriorationdue to sludge formation and which will be especially effective under conditions of extreme pressure.

Other-objects of the invention will appear as the description proceeds.

To the accomplishment of theforegoing and related ends, said invention, then, consists-of the means'hereinafter fully described andparticularly pointed out in the claims.

The following description sets forth in detail certain approved combinations of ingredients embodying my invention, such disclosed means constituting, however, but certain of various forms in which the principle of the invention may be used.

Broadly stated, this invention comprises incorporating at least one each of a halogenated oxygen-free organic compound and an oxygen-bearing organic compound, which for most purposes is also preferably halogenated, with an oil base.

As is hereinafter more particularly pointed out, the above-defined components of the lubricant comprising this invention will preferably and for best results have certain physical and chemical characteristics which especially adapt the same.

for use in conjunction with the principal types of engines in use today, and for other uses.

The solvent components of the lubricant should be .of fairly low volatility, i. e., with a vapor pressure at a temperature of 140 C. of below atmospheric, or preferably a vapor pressure less than atmospheric at a temperature of 170 C.

In one embodiment of my invention now in commercial use, one component of my new solvent has a vapor pressure less than atmospheric at a temperature above 300 C. A mixture of two components, one with a vapor pressure a little below atmospheric-at 170 C. and the other with a vapor pressure a little below atmospheric 8. 350 C., has proven highly satisfactory.

Oxygen-free component I have found that of the entire class of halogenated oxygen-free organic compounds usable as a component of the solvent constituent in my new lubricant, as above defined, the halogenated hydrocarbons and generally those of the aromatic series are to be preferred for most purposes as solvents for the unoxidized polymerized hydrocarbon deposit. Throughout this application, the term aromatic series is intended to include homologs as well. As hereinafter pointed out, however, certain of the aliphatic compounds of this type are particularly useful for certain purposes.

In the case of the halogenated aromatic oxygen-free compounds, it is generally preferable that the halogen be attached to a carbon atom of the benzenoid ring. These latter compounds are usually more desirable because of their noncorrosive character and general stability.

The halogenated oxygen-free organic compounds, as noted, may be either:

A. Aliphatic, such as halogenated:

I. Hydrocarbons, i I

Notably, those chlorinated or iluorinated hydrocarbons which contain from four to ten or more carbon atoms, e. g.

g. chlorinated or fluo- V. Merca tans e. g.

Chlo ated or fluorinated: Lauryl mercaptan Cetyl mercaptan Carnaubyl mercaptan Ceryl mercaptan 5 Montanyl mereaptan Melissyl mercaptan Myricyl mercaptan VI. Thiocyanates (rhodanates) e. g.

Chlorinated or iluorinated: Ethyl thiocyanate Butyl thlocyanate Lauryl thiocyanate Cetyl thiocyanate Ceryl thiocyanate or the more generally preferable:

B. Cyclic compounds, such as halogenated:

I. Benzene and related compounds such as: (l) Halogenated benzene, e. g.

(a) Chlorinated benzene, e. g.

The dienlorbenzenes, notably the ortho compounds ((2) Brominated benzene, e. g. Ortho-dibrom benzene (c) Fluorinated'benzene (2) Halogenated derivatives of benzene such as: 20 (a) Halogenated homologs of benzene, e. g.

Mono-cnlor toluene Monochlor xylene Mono-chlor cymcne Ethyl mono-chlor benzenes Propyl mono-chlor benzenes Di-ethyl dichlor benzenes Propyl dlchlor benzenes Di-ethyl tetrachlor benzenes Halogenated amino derivatives of benzene, c. g.

Chlorinated aniline Mono-chlor aniline (preferably the ortho-compound) Mono-chlor di-methyl aniline Chlorinated tolnidines Chlorinated xylidlnes Chlorinated diphenylamme (c) Halogenated nydrobcnzencs, e. g.

Hydrogenated dichlor-beuzenes Dichlorhexahydrobenzene (dlehlor cyclohexane) ll. Polyphenyls, and related compounds, including dipheuyl,

diphenyl benzenes, etc., such as, (l) Haiogenated diphenyl, e. g.

(a) Chlorinated diphenyl, e. g.

Mono-chlor diphenyls Di-cnlor diphenyls Tri-chlor diphenyls (b) Brominated diphenyl, e. g. The mono-brom diphenyls (c) Fluorinated diphenyl (2) Halogenated derivatives of diphenyl, such as,

(a) Halogeuated homologs of diphenyl, e. g.

Chlorinated phenyl-tolu nes Ethylated, or propylated, chlorinated diphenyl, e. g. di-ethyl tetrachlor diphenyl (b) Halogenated amino derivatives of dlphenyl, e. g.

Chlorinated phenylganilines Cnlorinatedpheny -toluidlnes Chlorinated diphenyl amines (xenyl amines) (c) Halogenated hydrodiphenyls, e. g.

Chlorinated phenyl hexahydrohenzene Chlorinated dodecahydrodiphenyl III. Naphthalene and related compounds, such as (l) Haloenated naphthalene (a) hlorinated naphthalene, e. g. a-Mono-chlor naphthalene (b) Bromlnated naphthalenes, e. g. a-Mono-brom naphthalene (c) Fluorineted naphthalene g2) Halogenated derivatives of naphthalenes, such as:

a) Halogenated homologs oi naphthalenes, e. g.

chlorinated methyl naphthalenes, such as a-methyl naphthalene Chlorinated ethyl, propyl, or isopropyl naphthalenes (b) Halogenated amino derivatives of naphthalene, e. g.

Chlorinated naphtbylamines Mono-chlor naphthyl amine (c) Halogenated hydronaphthalenes, e. g.

hlorinated decahydronaphthalene 6 Chlorinated tetrahydro naphthalene IV. Phenanthrene and enthracene and related compounds, such as (l) Chlorinated phenanthrene, chlorinated anthracene (2) Halogenated derivatives of phenanthrene and anthracene, such as: (a) homologs, e. g.

l-methyl phenanthrene 3-methyl phenanthrene 9,10 dimethyl henanthrene propyl 'and lsopropyl derivatives of such as retene anthracenes anthraoene anthracene and isopropyl derivatives of anthracene (b) Halogenated amino derivatives, e. g. Chlorinated phenanthrylamines Chlorinated anthramines (c) Halogenated hydrophenanthrenes and halogenated uh? ant scenes, e. g. O orinated retene 011 (contains hydro retene) V. Chrysene, picene, and related compounds, including their derivatives, such as homologs, amino derivatives and other substitution products. a

VII. Heterocyclic compounds, such as pyridine, quinoline,

conjunction with the solvents for the unoxidized polymerized hydrocarbon deposit, also being compatible with the oil. Here again, compounds of the aromatic series with the halogen attached to the ring are favored. However, a certain number of the oxygen-bearing aliphatic compounds have been found to be very eflective.

The oxygen-bearing components may,

for convenience, be classified as follows:

yrrole, thiophene, and derivatives of them, e. g., mono-ehlor 5 1. Aliphatic, or carbon chain ype Pyridmeoxyfieng derivatives of: VIII. Nitriles derived from any oi the above compounds, e. g A. ydrocarbons oi the paraflln series;

Chlorinated: B. Hydrocarbons oi the oleflne series; and

5 513 3 0. Hydrocarbons o! the acetylene series. 93' II. Organic ring type B I de Nfihg lfianide Oxygen-bearing derivatives of: Xenyl cyanide A. "Carbon ring" type compounds Cyclone! 11 (l) of the aromatic, or allied type, including oxygen-bearing IX. sulphides derived from any of the above compounds, e. g. derivatives of benzene, na hthalene, anthracene, etc., Chlor ted: also compounds of the bri ged ring type, such as the niphenyl sulphide terpenes, and related compounds. Dibenzyl sulphide 15 (2) o! the class including the cycloparaflins, cyclo-oleflnes, DiXylyl sulphides etc. Examples 0! this class are oxygen-bearing derivagi-naplligllililrl iuphides tives of the following:

7 P (a) H drogenation roducts of benzene (e.-'g. cyclo- Dicycloheryl sulphide hexane, cycle exene, cyclohexadiene), such as X. Mereaiptans derived from any of the above compounds, e. g. h drogenated phenol, notably Chlor nated: gholtifixaggl l Benzyl mercaptan y 0 mo Phenyl benzyl mercaptans 2o tetm'hydm phenol Naphthyl mercaptans (b) Hydrogenation products of naphthalene (e. g., Pbenyl propyl mercaptans decahydronaphthalene, tetra hydronaphthalene, Cyclohesyl mercaptan etc.), such as the hydrogenated naphthols. XI. Thiocyanates, e. g. (e) Naphthenes, such as naphthenic acid, etc.

Chlorinated: (3) 0! mixed type such as derivatives of indene, hydrindene,

Benzyl thiocyanate hydranthracene, etc. eny% ethyl g ifiwyanati B. "Heterocyclie" type compounds I any prom locyana e (1) Of the aromatic or allied type includin derivatives of Cyelohexyl thiocyanate pyridine, qumolme, em 5 2 h h It W111 be noted that tllie above enumergiiaed U igggit'gfii'gg gggggfgggggfgi i and examples of the organic I ng communds w ch 80 The oxygen-bearing derivatives of the foregoing are usually preferred are, in general, compounds compounds may also be classified according to the of the aryl type compounds containing nature of the attachment of the oxygen to the benzenoid ring structures and also of the type in molecule viz which the halogen is directly attached to an atom which is a part of such ring structure. Very sat- 85 I. Directly attached to one or more carbon atoms, as in the case of: isfactory results may be obtained when two or Ether-s and 4 compounds more different halogens are present in the same (2) ompunds molecule, ortho brom chlor benzene being a good & example of such a compound. If the aromatic compfmllds have been alkylated, y are often 40 radicle, such as alcohols and other derivatives of carbinoi espec ally e flective. (including phenols, cresols, naphthols, etc.)

As a matter of convenience the halogenated cmplmds Naming the carbmlyl diphenyls and substituted diphenyls, as well as halogenated substituted benzenes where two or more Phenyl groups are directly linkedmay be radicle, suchasaldeh des, k'etones, organic acids, esters Y inclusively referred to as halogenated polyand salts of organic acids, thin-acids and esters of thio-aclds h 1 (4') Compounds in which ox ggcinfltormsha pgrt of a rinfi sgrrucgurei Some or the best examples of the aromatic m',,., S my or y solvents are: (5') Compounds with an inorganic radicle where the oxygen diigcig yigetstached to a carbon atom, e. g. Ortho-dichlor benzene Mcno-chlor toluene ggg g Di-ethyl dichlor benzenes T R ms was researc e time 0|. 8 e BIIY Chlorinated el ylated diphenyl gogrgtgoxylmmes II. Indirectly attached through the means of some other atom i. e. Good examples of halogenated. aliphatic hymthemm ofmmmwlc Mme, drocarbons are: Ammo Chi Fluorinated entane Clil l d t Fluorinated exane Cyanate Fluorinated octane -Hydro: rylamine Halogenated petroleum derivatives, particularly halogenated petro- 6o itrate leum waxes. Ntrite N tro Oxygen-beefing component Perchlorate I have found that of the entire class of oxyfgfii t e gen-bearing organic compounds usable as a comulphlte ponent in my improved solvent, as above defined, flggggg acid the halogenated compounds and preferably those iulphonlc acid of the aromatic series, are generally superior solfil ggffg vents for the oxidized polymerized hydrocarbon Thiophos bite deposit, and that these solvents may be used in Tmwulp (Nole.Thia class includes salts of organic bases with inorganic oxy-acids.)

or unhalogenated, as the case maybe;

Organic oxygen compounds Ring compounds Unhalogenated Halogenated Aromatic:

Phenols Phenol O-chlor phenol a-Naphthol Monochlor a naphtho1 Amino henol Butylle enol Pheny phenol Resorcinol Chlor-resorcinols Xylenol "Tar acids" (preierably refined by distillation) Cyclohexyl phenol Alcohols Benzyl alcohol Chlor benzyl alcohols Phenyl ethyl alcohol Benzaldehyde Aldehydcs (less desirable because of polymerization) Ketones Acetophenone Monochlor acatophenone Benzophenone Monochlor benzophenone Alkylated benzophenones, a. g.: Alkylated chlor-benzophenones, e. g.:

Methyl benzophenones Methyl chlor-benzophenones.

Dimethyl benzophenones Dimethyl chlor-benzophenones Ethyiated benzophenones Ethylated chlor-benzophenones Propylated benzophenones Propylated chlor-benzophanones Phenyl tolyl ketones Dinaphthyl ketone Amides Acetanilide Stcaranilide l Stear-chloranilides Acids Aromatic fatty acids, e. g.:

. Phenyl acetic acid Chlorphenyl acetic acids Phenyl stearic acid Chlorphenyl stearic acids Salicylic acid Chlor-salicylie acids Esters and salts Phenyl acetate Ethyl chlorbenzoates Phenyl carbonate Butyl chlorbenzoates Ethyl benzoate Di-rnethyl ehlorphthalates Butyl benzoate Di-ethyl chlorphthalates Di-methyl phthalate Di-butyl chlorphthalates Di-ethyl phthalate Di-butyl phthalate Methyl salicylate Methyl chlor salicylates Benzyl acetate Chlorbenzyl acetates Pyridine acetate Quinolinc acetate Quinoline oleate Quiuoline stearate Pyridine stearate Esters and salts of aromatic fatty acids, Esters of chlor-aromatic fatty acids,

e. an: e. g.:

Esters of phenylacetic and phenyl- Esters of chlorplienyl acetic and stearic acids, including the chlorphenyl stearic acids includmethyl, ethyl, butyl, lauryl, mg the methyl, ethyl, butyl, cetyl and ceryl esters; sodium lauryl, cetyl and ceryl esters; and calcium phenyl-stearate. sodium and calcium chlorphenyls cara es Ethers Diphenyl ether Chlorinated diphenyl ether Pheuyl ethyl ether Chlorphenyl ethyl ethers Dixenyl ether Chlorinated dixenyl ether Dinaphthyl ether Chlorinated dinaphthyl ether Alkylated diphenyl ether Alkylated chlor-diphenyl ether Non-aromatic oxygen-bearing organic ring compounds Cyclo-hexanol r Cyclo-hexyl esters, e. g. cyclo-hexyl stearato, cyclo-hexyl laurate,

tri-cyclo-hexyl phosphate, tri-cyclo-hexyl phosphlte Naphthenic acids Esters of naphthenic acids, e. g. methyl naphthenates Oxygen-bearing heterocyclic compounds esters of thio hene carboxyllc acids and esters of pyrrole carboxylic ac ds.

gg g Unhalogenated Halogenated Alcohols Octyl alcohol Fluorine ted octyl alcohol Decyl alcohol Fluorlnated decyl alcohol Lauryl alcohol Fluorinated lauryl alcohol Cetylalcohol Fluorinated cetyl alcohol Carnaubyl alcohol Fluorinated carnaubyl alcoh ol Cerylalcohol Flfiiorinated ceryl co Montanyl alcohol Fluorinated montenyl alcohol Melissyl alcohol Fluorinated melissyl alcohol Myricyl alcohol Fluorinated myricyl alcohol Esters and salts-. Methyl palmitate Mtethyl dichlor palmia e. Methyl stearate Methyl dichlor stearate Methyl lactate sodium chlorhydroxy Butyl lactate stearate La ,1 acetate Cety acetate 3 8 Unhalogenated Halogenated Ceryl acetate Tri-ethanol-amine acetate Tri-lauryl phosphate Tri-lauryl phosphite Di-ethyl oxalate Di-butyl oxalate Di-laur loxalate Di-cety oxalate Di-ceryl oxalate Dimethyl malonate Dibutyl malonate Dimethyl succinate Dibutyl succinate Dimeth-yl tartrate Dibutyl tartrate Dilauryl tartrate Hydroxy-amines. Tributyl citrate Trilauryl citrate Tri-ethanol amine Ethers Tri-butanol amine Dibutyl ethanolamine Butyl ether Chlorinated or fluor- Amyl ether inated: Octyl ether Ethyl ether (no- Lauryl ether tably 5, B dichlorethyl ether) Butyl ether Amyl ether Ketone Dipropyl ketone Chlorinated or fluor- Dibutyl ketone inated: Dl-amyl ketone Laurone Dl-oetyl ketone ,Palmitone Laurone Stearone Palmitone Stearone Acids. Propionic acid Chlorinat or fluor- Butyric acid 'inate Lauric acid Lauric acid Palmitic acid Palmitic acid Stearic acid Stearic acid Hydroxystearic acid Chlpdrhydroxysteario aci diphenyl ether which contains about six atoms of chlorine permolecule, and has preferably been purified by vacuum distillation, or other means, is one of the most desirable solvents of this class. This solvent boils at a temperature above 300 C. without appreciable decomposition. (See my co-pending application Ser. No. 83,976.)

Of theabove enumerated classe of oxygenbearing compounds, the aromatic compounds are generally preferred and particularly the aromatic ethers and ketones. Another preferred class of compounds is that in which oxygen forms a part of a ring structure. In the case of unhalogenated oxygen-bearing organic compounds, particularly for use in crank-case lubricants, they should preferablyboil at atmospheric pressure without appreciable decomposition.

Sincearomatic compounds containing multiple ring structures of the condensed type such as naphthalene, anthracene, phenanthrene, etc. (that is, of the type in which certain carbon atoms "are contained in or common to two rings) are more easily oxidized, and, therefore, less stable than the non-condensed multiple-ring type in which no carbon atoms are thus shared, the latter type is to be preferred. Poly-nuclear aromatic compounds (that is, those containing more than one ring) of the non-condensed type are thus the more desirable of such aromatic compounds.

It is to be noted that certain compounds of the class in which oxygen is in the form of an inorganic radicle, have the additional advantage of inhibiting corrosion, and, therefore, otherwise corrosive halogenated oxygen-free organic compounds may be used in conjunction with them for service in lubricants. Notable examples of such compounds are the organic phosphates, of which tri-phenyl phosphate and tri-cresyl phosphate are good examples, and the phosphites, such as tricyclohexyl phosphite, tri-phenyl phosphite and the alkylated aromatic phosphites. Other examples of such compounds will be found in my co-pending applications Ser. Nos. 99,165

' filed September 2, 1936, and 119,132 filed January 5, 1937. However, with these exceptions, the

'of the individual examples of compounds listed herein may be used alone as the sole addition to the hydrocarbon oil to efl'ect considerable improvement in sludge-solv'enticity, as well as other properties of the oil aflecting its use as alubricant. All of the halogen compounds, for example, are effective extreme pressure addition agents and the oxygen compounds are more or less .effective to improve oiliness.

Preferred combinations to make up my new solvent include:

About 25% to 75% o-dichlor benzene, ethyl chlor-benzenes, ethyl dichlor benzenes, or diethyl tetrachlor benzenes, with one or more of the following:

Hexachlor diphenyl oxide Trichlor dighenyl oxide Monochlor enzophenone Benzo henone Methy benzophenones Methyl chlorbenzophenones Phenyl acetate ghellllol l h l -p eny p eno Cyclo hexanol Dibutyl phthalate Methyl salicylate Lauryl alcohol Methyl steal-ate Tri-ethanol amine Trl-ethanol amine acetate The chlorinated diphenyl oxide and other compounds referred to above are compounds containing an average number of chlorine atoms equivalent tothat indicated.

In cases where the lubricant is to be exposed a to relatively high temperatures, it is of particular advantage to use compounds for both components of my new solvent which are highly stable. For use in the crankcases of internal combustion engines, it will usually be preferable to employ compounds which will not be subject to thermal decomposition when the lubricant is exposed to temperatures as high as C., and more desirably C. or even 200 C.' It is frequently advisable to employ compounds which will boil at atmospheric pressure without appreciable decomposition, preferably at temperatures above 140 C., or more desirably 170 C. or even 200 C.

Chlorine, bromine, and fluorine are the halogens most desirable in both the oxygen-free and oxygen-containing compounds, fluorine forming particularly stable compounds which are no longer so diflicult to prepare as formerly. Methods ofpreparing fluorine compounds which will be found satisfactory for use in my solvent are described, for instance, in U S. Patent No. 2,013,030, Example IV, and in U. S. Patent No. 2,013,050, Example X. My invention, of course, is not to be considered as involving any particular method of preparation of the components nor is it intended to be limited by any such method or methods. Chlorine is the least expensive and mostcommercially available of all the halogens, and bromine is also satisfactory, although considerably more expensive, as is iodine.

The action of my new solvent composition may sometimes be improved by the use of a more or less complex mixture in the case of one or both of the two components used. This complexity may result from (1) the production of a plurality of compounds obtained by the halogenation process, as, for example, the chlorination of di-v phenyl' or of diphenyl ether, either of which is capable of producing a large number of chlorinebearing compounds difiering as to the number and location of the chlorine atoms in the molecule; or (2) the use of a product which, before halogenation, isa complex organic material, such as: (a) chlorinated petroleum fractions; chlorinated paraffin wax; chlorinated commercial aromatic hydrocarbon products, such as mixed toluenes and xylenes, dead oil," and the like; for the halogenated oxygen-free component; and (b) non-drying fatty oils, such as sperm oil ;'-'tar acids; and esters derived from mixed alcohols, such as lorol; for the oxygen-bearing com: ponent.

It is also of advantage to use a combination of solvent components which will have a fairly wide range 1 of volatility. uniform solvent action, even if some of the com pectedly hightemperatures.

This-assures a. certain and The oil base The lubricating oil which constitutes the oil base of my improved lubricant as noted above may be any mineral lubricating oil or synthetic equivalents. For use. in the crankcases of internal combustion engines, the oil base will preferably be a highly refined mineral oil or synthetic hydro-carbon oil, and usually within the viscosity range of from about to about 160 seconds Saybolt at 210 F., and more often within the range of to 80.

Drastically refined oils, including those which have been solvent-extracted, the properties of which have been greatly improved for certain uses, are now available. The particular properties which it has been found possible to improve by such methods are, among others, the viscosity index and the sludge" forming tendency of the oil. However, oils of this type, when subjected to heat and oxidation, are still subject to the tendency to precipitate a resinous or varnishlike coating on the metal parts with which the oil comes in contact. This tendency is particularly serious in the crankcase lubrication of heavily loaded or high-speed internal combustion engines, notably of the aviation and Diesel types where the lubricant is exposed to relatively high temperatures.

For gear lubrication, the mineral oil need not be so highly refined and even so-called black oils are sometimes used. However, it is usually preferable to use a reasonably well-refined oil such as steam-refined or bright stock, or blends methods, particularly various modifications of the solvent-extraction type of refining process, have made it possible to produce oils of almost any desired viscosity index from any of the other crudes. For example, solvent-extracted oils from Coastal crudes with viscosity indices (Dean and Davis) from about to about 90, and from Mid- Continent crudes with viscosity indices of from about 90 to about 110 are now commercially available. The same type of process, applied to oils obtained from Penns'ylvania crudes, has produced oils with a viscosity index ranging from about 100 to about 120, or even higher.

As noted above, these oils may also have the sludge" fomiing tendency greatly reduced but are still susceptible to the formation of varnishlike deposits. For this reason, the Mid-Continent or naphthenic oils, refined by the more conventional methods, are still to a considerable extent, preferred for use where the resinous type of deposit is particularly undesirable as in the lubrication of Diesel engines, particularly those operated under high loads or at high temperatures. For certain usespf this type, it is considered more desirable to use an oil which may, to a certain extent, be sludge forming but will not have the disadvantage of sticking rings or pistons because of its tendency to form resinous deposits.

Mineral oil of this type is now widely used for this purpose, and more recently in conjunction with detergent materials, such as oil-soluble soaps; which have been added insmall amounts to further overcome the ring sticking tendency of the oil.

The solvent combination of my invention is useful in improving oils of the highly refined type, such as those generally used in crankcase lubrication, and likewise to improve the less highly refined oils usually used in gear lubrication. It is useful both in overcoming the tendency of the refined Pennsylvania and solvent-extracted types of oils to fonm varnish-like deposits, and to overcome the tendency of the naphthenic type oils to form sludge." It may also be used to advantage in conjunction with detergents such as those described above. It should be noted that one or both of the components of my solvent may be of the type which also has detergent properties.

It is to be understood that among the oils which may be used as the base of my improved compositions are included hydrogenated as well as voltolized oils.

As the exact manner in which my solvent constituents act upon the sludge is not entirely understood, I do not intend my invention to be restricted by any explanation or theory. However, it seems that the two types of solvents mutually aid one another in attacking the gummy sludge for it has been found that the effectiveness of their joint action is more than the cumulative effect of the two when used separately.

The presence of the halogen lowers the volatility and thus enables the use of a number of the most effective solvents which would otherwise be too highly volatile at engine temperatures. The presence of the halogen also notably enhances the solvent action of the compounds and therefore makes available more effective compounds. The degree of halogen-ation may, however, reach an optimum beyond which further halogenation gives no improvement in the solvent action or may even cause a decline in effectiveness.

The relative proportions of halogenated oxygen-free organic constituents and oxygen-bear.- ing organic constituents in the new solvent comprising my invention may vary within wide limits, depending upon the particular materials used (a very minor proportion of the more active components at times being quite effective), the kind of oil to which the solvent is to be added, and the kind of engine employing the lubricant The ,ratio of the amount of halogenated oxygen-free organic constituents to the amount of oxygenbearing organic material usually may vary from about one to ten, up to about ten to one, but preferably only from about one to two, up to two to one. For most applications a lubricating composition containing a solvent comprising substantially equal amounts of each type has been found very satisfactory.

The amount of the solvent combination to be added to the oil will depend upon the type of oil and the type of engine using the lubricant, and may vary over wide limits, for example, from about .001 to about 20% by weight based on the oil. To obtain a maximum of desirable characteristics in the lubricant, a proportion of from about .1% to about 3% of the combined solvent is usually of advantage while amounts up to 5 or 10% are occasionaly desirable and amounts up to 20% may often be used without unduly decreasing the viscosity of the lubricant.

aid in removal of oil sludge."

Proper stability of the components of the solvent combination in the lubricant is an important factor. Since the materials are to be exposed to relatively high temperatures in the crankcase, etc., they should be particularly resistant to thermal decomposition.

Resistance to hydrolysis is a most desirable characteristic because of the likelihood of a certain amount of moisture being present in the crankcase. Under these conditions, easily hydrolyzed halogen compounds will tend to produce hydrogen halides which will cause corrosion of the parts of the engines with which they come in contact, although this tendency may be corrected to a certain extent by the use of proper inhibitors.

Elsewhere in this specification reference is made to the fact that the specifically identified addition agents contemplated for usemay be incorporated in the lubricating composition of my invention in amounts up to 20% or for certain uses, in less amounts, for example, up to 10% or up to p Among the large number of clas e of pounds disclosed herein will be found specific examples which are not fully oil-soluble to the extent of the percentages above stated. Certain of such compounds will be soluble to only a minor least one of the solvents be of the aromatic series. The two solvent compositions described have a cooperative dissolving effect, each enabling the other to work more quickly and completely.

This invention is equally applicable to other than automotive fields of lubrication and other uses for my improved lubricant will be immediately apparent to those skilled in the art. This invention is intended to cover all such applications.

It is also to be noted that combinations of the extent, for example, on the order of about 1%,

and they, of course, are useful for the purpose herein specified up to the extent of their solubility. Still others are difilcultly soluble to any extent, even minor, and require the use of special blending apparatus or even mutual solvents in order to embody the same in a composition in such form as not to separate out. Among the large class of compounds identified will also be found certain specific examples which may not be soluble in mineral oil to :any extent. Those will obviously not be useful for my purpose.

Throughout the specification and the claims, therefore, I have employed the term "oil-soluble as being a further limitation on the compounds which are useful in the compositions of my invention. Where the compound is soluble to only a limited extent, 1. e., less than the range specified within which the same may be employed, it

use in automobile, truck and bus engines. The.

solvent constituents may be most conveniently introduced into the mineral oil before such oil is placed in the crankcase, but thi invention does not cover nor is it intended to be limited by any particular method of addition of the solvent constituents to the lubricant. Any practicable means of addition is intended to be within the -scope of this invention. Other specific-applications of thisinvention have been made and will occur to those acquainted with the art and this invention is intended to include all such applications.

To a mineral oil base are, therefore, added my .solvent constituents comprising at least one representative of each of the two types of compounds disclosed to inhibit the formation and It is generally preferable, but not absolutely necessary, that at The following are specific examples of lubricating compounds, in accordance with my invention, particularly useful as crankcase lubricants in internal combustion engines. These same compositions may advantageously be used also as spindle oils, hydraulic oils, compressor oils and the like, particularly under conditions which expose the lubricant to oxidation at high temperatures.

The base oil will preferably be a Pennsylvania motor oil (or other oil of high viscosity index) having a viscosity such that it will meet the speci fications for an S. A. E. 10, 20, 30, 40, or

.motor oil. For crankcase lubrication, in most thenic base oils.

In the following examples of lubricating compositions, I shall indicate only those addition agents, the use of which is the particular subjectmatter of the present invention. It will be understood that in each such specific example, the remainder of the composition is substantially all mineral lubricating oil of the character above defined with the possible addition of minor amounts of further constituents such as means for improving the'cold test, etc., as are commonly employed in lubricating compositions of this character.

Methyl salicylate 0.01

Example 5 Example 20 Percent Percent Orthodichlor benzene 0.5 Orthodichlor benzene 0.5 Hexachlor diphenyl oxide 0.5 Hexachlor diphenyl oxide 0.5 Calcium phenyl-stearate 1.0 -Tri-cyc1ohexy1 phosphate 0.2

Example 6 Example 21 Orthodichlor benzene 0.5 Orthodichlor benzene; 0.5 Hexachlor diphenyl oxide 0.5 Hexachlor diphenyl oxide 0.5 Calcium chlorphenyl-stearate 1.0 Butyl acetyl ricinoleate 0.25

' Example 7 Example 22 Orthodichlor benzene 0.5 Orthodichlor benzene 0.5 Hexachlor diphenyl oxide 0.5 Hexachlor diphenyl oxide 0.5 Cyclo-hexyl stearate 0.5 Di-ethylene glycol dichlorstearate (mono- Example 8 ester) 0.06 Orthodichlor benzene 0.5 Example 23 Hexachlor diphenyl oxide 0.5 Orthodichlor benzene 0.5 Methyl phenyl-stearate 0.5 Hexachlor diphenyl oxide 0.5 Example: 9 f Cyclohexyl phenyl-stearate 0.5 Orthodichlor benzene 0.5 Example 24 Hexachlor diphenyl oxide 0.5 Orthodichlor benzene 0.5 Methyl chlorphenyl-stearateuxx 0.5 25 Hexachlor diphenyl oxide 0.5 Example 10 Cyclohexyl chlor-phenyl stearate 0.5 Orthodichlor benzene 0.5 Example 25 I Hexachlor diphenyl oxide 0.5 Orthodichlor benzene 0.5 'Benzophenone 0,25 HBXaChIOI diphenyl oxide 0.5

Example 11 Methyl chlorbenzoate 0,25 Orthodichlor benzene 4).5 Example 26 Hexachlor diphenyl oxide 0.5 o-Dichlor benzene 1.0 Methyl benzophennne 025 Butyl stearate 0,5

Example 12 p Y Example 27 Orthodichlor benzene 0.5 Oh10r bPnZPnP 0.4 Hexachlor diphenyl oxide 0.5 Triphenyl p sphite 0.13 Di-ethyi diphenyloxide 0,5 e achlor diphenyl oxide 0.4

, Example 13 Emmple 28 Orthodichlor benzene 0.5 h10r benzene 0.3 Hexachlor diphenyl oxide 0,5 l h xyl phosphite 0.06 Dimethyl phthalate ,5 Hexachlor diph nyl oxide z 0.3

' Example 14 4 Example 29 Orthodichlor benzene 0.5 -p r n ene 0.25 Hexachlor diphenyl oxideu 0, r syl phosphate x 0.03 Dibutylphthalate 0,5 hlor diphenyl oxide 0,25

Example 15 Q Example 3 Orthodichlof benzene 05" lo'Dichlor bpnmmp' 0.15 Hexachlor diphenyl oxide 0.5 j Phosphate? 0.03 Methyl salicylate [L13 Tn'Phenyl Rhosphlte 0.16 Hexachlor diphenyl oxide 0.15 Emmpze 16 Example 31 Orthodichlor benzene 0.5 ov-Dichlor benzene. 1.0 Hexachlor diphenyl oxide 0.5 Methyl stearate 0.5 Methyl chlorbenzophenone 0.13 Hexaohlor diphenyl oxide 0.5 Example 17 Example 32 o-Dichlor benzene 025 Orthodichlor benzene 0.5 Hexachlor diphenyl oxide 0.5 Methyl dlchlor benzophenone 0.25 Cyclohexyl salicylate 0,13 7 Example 33 E l 18 i 0-DiCh10l bPnzene 0 4 mmp 6 Methyl salieylafe 02 Orthodichlor benzene 0 5 Hexachlol yl ide 0.4 Hexachlor diphenyl oxide; 05 Methyl icylate 0.2 Cyclohexyl chlorsalicylate 0.13 Example .34

Example 19 O-Pichlor benzene 0.25 Dl-ethyl tetrachlor benzene 0.25 orthodichlor benzene 0.5 Methyl stearate 0,25 'Hexachlor diphenyl oxide 0.5 Butyl steal-ate 03 Tn-cyclohexyl phosphlte 0.1 Hexachlor diphenyl oxide; 0.5-

Methyl dichlorstearate 2,330,288 9 Example 35 Example '50 Percent Percent Dl-ethyl tetrachlor benzene 0.5 o-Dichlor benzene 0.25 Hexachlor diphenyl oxide; 0.5 Di-ethyl tetrachlor benzene 0.25 Methyl dichlorstearate 0.25 5 Methyl dichlorstearate 0.25

Example 36 Ewmple 51 0.5 Dl-gthy] tetrachlor benzene 0.5 D ethyl Petracmor benzene Hexacmor diphenyl oxide ()5 Methyl dlchlorstearate Cyclohexyl dlchlorstearate 0.2 (Note.Hexach1or dlphenyl oxide, referred to 37 in the above examples, consists of the vacuum Example distilled fraction of chlorinated diphenyl oxide Di-ethyl tetrachlor benzene 0.5 which has an average of sixchlorine atoms per Methyl chlor-salicylate 0.25 molecule.)

Specific examples of lubricating compounds ac- Example 38 cording to my invention, which are suitable for Di-ethyl tetrachlor benzene 0.5 .use in gear lubrication and the like, ar as 01- Cyclohexyl chlor-salicylate 0.25 lows: i

. The base oil in this case will be'a gear o l hav- Emmzole ing a viscosity such "that it will meet with the Di ethy1 tetrachlor benzene 05 specifications for S. A. E. number 80, 90, 110, 160 Hexacmor dipheny] oxide 0, r 0 ar il and may be prepared by blending Calcchlorhen Lsteamte 11 two or more stocks consisting of bright stocks, mm p y steam-refined stocks or neutral oils, to give the Ezample 40 25 desired characteristics. In most cases, I prefer m r n 05 for my purpose a base oil which has a relatively fiff fi ffifi f 05 gh viscosity index such-as may be obtained by 05 using Pennsylvania oils. Cyclohexyl chlor phenyl steamte Similarly as in connection with the examples Example 41 of lubricating compositions which have been found useful as-crankcase lubricants I shall in- 0.5 v. 3 21 5 gi ggg igg ggg 1.0 dicate in the following examples of gear lubri- Hexacmor diphenyl oxid; 05 nts only those addition agents about which the present inventionis primarily concerned. It is t Example 42 be understood, of course, that the gear lubricants 0 given below may contain, in addition to the mino-lDichlor benze e eral oil specified above to make up the entire DI-ethyl tetlzachlo-r benzene composition, minor amounts of other constituents Hexacmor mphenyl oxide such as are commonly employed in gear 1mm- Methyl dichlorsteamte 1 cents, for example, thickening nt such as E m I 43 soaps, etc. p 6 Example 52 O-DichlJr benzene Per cent Chlorinated diphenyl (48% Cl) Chlorinated paramn wax (containing about Methyl stearate -5 45 40% chlorine) 3 7 Example 44 I Butyl stearatp I 1 Exam 1 Chlorinated diphenyl (48% c1) 1.0 p e 53 Hexachlor diphenyl oxide 0.5 l a d paraflin wax 6 Tricresyl phosphate ;a 1 45 1 0 Example 54 Chlorinated diphenyl- (48% Cl) oxide 3*iiir3i $ffii 1f::::::::::::::"'31:: i1 chlorhsaucyslaxg 55 Tri cresy1 phosphate? 1 Example 46 Example 55 Chlorinated diphenyl (48% Cl) Chlorinated paramn wa,x 8 H xac or d p e y xides Di(chlorbenzyl) disulphideufi 2 Calcium chlor-phenyl-stearate 6o Tricresyl phosphate 1 p Example 47 F 7 Example 56 o-Dich1or benzene 0.5 Chl rinat d paraffin wax 7.5 Ethylated chlorinated na hthaiene 0.5 Chl rb nzyl thlocyanate 1.5 Methyl steal-ate 0.5 Tn resy ph sp ate 1 Example 48 1 Example 57 n Chlorinated paraflln wax 8 -Di hlor b one 0.5 g g f m naphthalene Tricresyl thiophosphate, a one's Hexachlor diphenyl oxide 0.5 7 The lubricating compositions of the present l 49 invention will be found admirably suited as adm dition agents for internal combustion engine Ethylated chlorinated naphthalene 1.0 fuels. When the fuel to which these com- Hexachlor dlphenyl oxide 0.5 pounded lubricants are added is a, liquid hydro- 035 carbon boiling within the gasoline range the lubricating composition will preferably contain a total of from about 2% to about and even up to about of the addition agents, i. e. the halogen-bearing oxygen-free organic compound and the organic oxygen compound which characterize the lubricating compositions referred to above. Such compounded lubricant is then added to the lighter hydrocarbon fuel in quantitiesvarying from about 0.05% to about 1.50% by volume. The optimum amount of lubricant added to the fuel will be found to be in the vicinity of about 0.30%, i. e. in the range from about 0.15% to about 0.60%.

Other modes of applying the principle of my invention may be employed instead of the one explained, change being made as regards the materials employed, provided the ingredients stated by any of the following claims or the equivalent of such stated ingredients be employed.

I, therefore, particularly point out and distinctly claim as my invention:

1. A lubricating composition comprising at least 80% refined mineral lubricating oil with the gum solvent properties of such composition improved by incorporating therein a total of from about .1% to about based on the amount of mineral lubricating oil of both an oil-soluble halogen-bearing hydrocarbon and an oil-soluble organic oxygen compound, said compounds being of .the type which will not substantially evaporate from such lubricating composition at ordinary temperatures.

2. A composition in accordance with claim 1 in which the oxygen-bearing compound is a ring compound.

3. A composition in accordance with claim 1 in which the oxygen-bearing compound is an arcmatic compound.

4. A composition in accordance with claim 1 in which the oxygen-bearing compound is an alkylated aromatic compound.

5. A composition in accordance with claim 1 in which the oxygen-bearing compound is an arylated aliphatic compound.

6. A composition in accordance with claim 1 in'which the oxygen-bearing compound is an arc-- matic ester. I

7. A composition in accordance with claim 1 in which the oxygen-bearing compound is an ester of an aromatic acid.

8. A composition in accordance with claim 1 in which the oxygen-bearing compound is an ester of a halogen-bearing aromatic acid.

9. A composition according to claim 1 in which the halogen bearing hydrocarbon is an alkylated aromatic hydrocarbon.

10. A composition according .to claim 1 in which the halogen bearing hydrocarbon is. a polynuclear aromatic hydrocarbon or the non-condensed ring type.

11. A composition according to claim 1 i which the halogen bearing hydrocarbon is a chlorine bearing hydrocarbon.

12. A composition in accordance with. claim 1 in which the oxygen bearing compound is an aromatic compound containing the carbonyl radical.

13. A composition in accordance with claim 1 in which the oxygen bearing compound is an ester of chlorsalicyclic acid.

14. A composition in accordance with claim 1 in which the oxygen bearing compound is a methyl ester of chlorsalicyclic acid.

15. A composition in accordance with claim 1 in which the halogen bearing hydrocarbon is an alkylated aromatic hydrocarbon and the oxygen bearing compound is a methyl ester of chlorsalicylic acid.

16. A composition according to claim 1 in which the halogen bearing hydrocarbon is a polynuclear aromatic hydrocarbon of the non-condensed ring type and the oxygen bearing compound is an alkylated aromatic compound.

17. A composition in accordance with claim 1 in which the halogen bearing hydrocarbon is a chlorine bearing hydrocarbon and the oxygen bearing compound is an arylated aliphatic compound.

18. A composition in accordance with claim 1 in which the halogen bearing compound is a cyclic hydrocarbon compound.

19. A composition in accordance with claim 1 in which the halogen bearing compound is a hydrogenated aromatic hydrocarbon compound.

in which the oxygen compound is an-ester of a monohydric alcohol.

23. A composition in accordance with claim 1 in which the oxygen compound is an ester of an aliphatic acid.

24. A composition in accordance with claim 1 in which the oxygen compound is a chlorbenzyl stearate.

25. A composition in accordance with claim 1 in which the oxygen compound is a methyl ester.

26. A composition in accordance with claim 1 in which the oxygen compound is an ester of a halogen-bearing aliphatic acid.

27. A composition in accordance with claim 1 in which the oxygen compound is methyl dichlorstearate.

28. A lubricating composition comprising at least refined mineral lubricating oil with the gum solvent properties of such composition improved by incorporating therein a total of from about .1% to about 20%, based on the amount of mineral lubricating oil of both an oil-soluble halogenated mononu'clear aromatic hydrocarbon and an oil-soluble organic oxygen compound, said compounds being of the type which will not substantially evaporate from such lubricatin composition at ordinar temperatures,

29. A lubricating composition comprising at least 80% refined mineral lubricating oil with the gum solvent properties of such composition improved by incorporating therein a total of from about .1% to about 20%, based on the amount of mineral lubricating oil of both an oil-soluble chlorinated alkylated benzene and an oil-soluble organic oxygen compound, said compounds being of the type which will not substantially evaporate from such lubricating composition at ordinary temperatures.

30. A lubricating composition comprising at least 80% refined mineral lubricating oil with the gum solvent properties of such composition impro\ ed by incorporating therein a total of from 31.- A lubricating composition comprising atleast 90% refined mineral lubricating oil with the gum solvent properties of such composition improved by incorporating therein a total of from about .1% to 20%, based on the amount oi mineral lubricating oil of both an oil-soluble halogenated hydrocarbon containing the diphenyl nucleus and an oil-soluble organic oxygen compound, said compounds being of the type which will not substantially evaporate from such lubricating composition at ordinary temperatures.

32JA lubricating composition comprising at least 80% refined mineral lubricating oil with the gum solvent properties of such composition improved by incorporating therein a total of from about .1% to about 20%, based on the amount of mineral lubricating oil of both chlorinated diphenyl and an oil-soluble organic oxygen c0m= pound, said compounds being of the type which will not substantially evaporate from such lubricating composition at ordinary temperatures.

- 33. A lubricating composition comprising at least 80% refined mineral lubricating oil with the gum solvent properties of such composition improved by incorporating therein a total of from about .1% to about 20%, based on the amount of mineral lubricating oil of both an oil-soluble halogenated hydrocarbon containing the cyclohexyl nucleus and an oil-soluble organic oxygen compound, said compounds being of the type which will not substantially evaporate from such lubricating composition at ordinary temperatures.

34. A lubricating composition comprisin at least 80% refined mineral lubricating oil with the gum solvent properties of such composition improved by incorporating about .1% to about 20%, based on the amount of 'mineral lubricating oil or both chlorinated methylcyclohexane and an oil-soluble organic oxygen compound, said compounds being of the mineral lubricating oil of .phenyl and type which will not substantially evaporate from such lubricating composition at ordinary temperatures.

35. A lubricating composition comprising at least 80% refined mineral lubricating oil with the gum solvent properties of such composition improved by incorporating therein a total of from about .1% to about 20%, based on the amount of both di-ethyl tetrachlorbenzene and a methyl esterpf chlor-salicylic acid, said compounds being of the type which will not substantially evaporate from such lubricating composition at ordinary temperatures.

36. -A lubricating composition comprising at least 80% refined mineral lubricating oil with the gum solvent properties of such composition improved by incorporating therein a total of from about .1% to about 20%, based on the amount of mineral lubricating oil of both chlorinated dia chlor-benzyl stearate, said compounds being of the type which will not substantially evaporate from such lubricating composition at ordinary temperatures.

37. A lubricating composition comprising at least 80% refined mineral lubricating oil with the gum solvent properties of such composition improved by incorporating therein a total of from about .1% to about 20%, based on the amount of 80-mineral lubricating oil of both chlorinated therein a total of from 35 aromatic.

methyl-cyclohexane and methyl dichlorstearate,

said compounds being of the type which will not substantially evaporate from such lubricating composition at ordinary temperatures.

38. A composition in accordance with claim 1 in which the halogen-bearing hydrocarbon, is

CARL F. rRU'r'roN.

read Certificate of Correction Patent No. 2,330,238. September 28, 1943.

CARL F. PRUTTON.

It is hereby certified that errors appear inthe printed specification of the above numbered patent requiring correction as follows: Page 4, in the table identified as Organic oxygen compounds strike out the word Benaaldehyde appearing in the third column headed *Halogenated and insert the same m the second column headed Unhalogenated op osite Aldehydes (less desirable because of polymerization);

same page, near the ottom thereof, for that portion of the table reading Hydroxy-amines Tributyl 'citrate Trilauryl citrate Tri-ethanol amine Ethers Tr'i-butanol amine Dibutyl ethanolamine 'Butyl ether Tributyl citrate Trilauryl citrate Hydroxy-amines Tri-ethanol amine Tri-butanol amine Dibutyl ethanolamine .Ethers Butyl ether page 11; first column, line 1, claim 31, for 90% read 80% and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 9th day of November, A. D. 1943.

a [slum] HENRY VAN ARSDALE Acting Commissioner of Patents. 

